Azo dyestuffs and process of making same



Patented Aug. 21, 1928.

UNITED STATES PATENT OFFICE.

HERMANN WAGNER, OF SODEN, AND OTTO SOI-IST, OF HOCHST-ON-THE-MAIN, GER- MANY, ASSIGNORS, BY MESN E ASSIGNMENTS, TO GRASSELLI DYESTUEF CORPORA- TION, OF NEW YORK, N. Y'., A CORPORATION OF DELAWARE. I

AZO DYESTUFFS AND PROCESS OF MAKING SAME.

Nio Drawing. Application filed March 12, 1925, Serial No. 15,121, and in Germany larch 29, 1924.

We have found that by coupling the hitherto unknown 2amino-4-aroylamino-l-alkyloxy- .aryloxy-. or aralkyloxy-benzenes (obtainable by the action of aroylchlorides upon 2-nitro-4-amino-1-alkyloxyaryloxyfor aralkyloxy-benzenes' and subsequent reduction) with any 2.3 hydroxynaphthoic acid arylides, beautiful claret-red dyeings of excellent fastness to light and kier-boiling are produced. Fast dyeings in such shades could hitherto not at all be obtained by means of monoazo dyestufls. I

In our newprocess there may,-for instance, be used with advantage the 2-aminol-benzoyl-amino-l-anisol which melts at 139. Similar dyestuifs may be obtained by using instead of benzoylchloride its homologue-s or substitution products, such for instance as chlorbenzoylehloride, alkyloxy-benzoylchloride or the like, for the preparation of the body to be employed as the diazo component or by substituting forthe methoxy group the ethoxy-, benzyloxyorphenoxy group.

The new dyestufls may be produced both on the fibre and in substance in presence or absence of a substratum. When produced in substance, they form claret-red powders, those prepared by means 'of phenyl-ethers having a somewhat redder hue than the others. They dissolve in sulfuric acid of 66 B. to an intense bluishviolet solution.

The following'e'xamples serve to illustrate our invention more fully, but are not intended to limit the same:

1.- 242 parts of 2-amino-i-be'nzoylamino-1- anisol are diazotized in the usual manner in a hydrochloride solution with 70 parts of nitrite and the diazo-solution so obtained is coupled with an alkaline solution of 2.3-hydroxynaphthoic acid-5-chloro-o-anisidide for instance as heavy spar (barium Sulfate). The. dark-red precipitate is filtered off,

washed and dried. The resulting dyestufi has most probably the formula:

sol are dissolved in com. of hot water and 5.2 ccm. of hydrochloricacid (22 B.). The resulting solution is cooled by the addition of 50 gr. of ice, and the cooled solution is mixed wit-h a solution of 1.44. gr. of sodium nitrite in 10 com. of water. The whole is then made up with water-to 1 liter and, before use, is neutralized with 4 gr, of sodium acetate.

The resulting dyed yarn is wound off, well washed, and soaped while boiling.

In this way a bright claret-red shade with a blue hue of excellent fastness to washing and kier-boiling is obtained. The dyestufi thus produced has the probable formula:

If for the 2.3-hydroaynaphthoic acid-4tchloro-2-toluidide is substituted 2.3-hydroxynaphthoic acid-5-chloro-2-anisidide NH:@CH :Cl=1:2:5 a claret-red shade of a still more bluish hue is obtained. a

3. Material is padded With an aqueous solution containing, in 1 liter, 242 gr. of 2.3-hydroxynaphthoie acid-5-chloro-2-anisidide (NH:OCH :Cl=1:2:5),

20 gr. of para soap P. N., and 80 com. of 22 Be. caustic soda solution. The padded material is dried, and thereafter printed with a dye composition prepared as follows:

24.2 gr. of 2-amino-tbenzoylamino-l-anisol are made into a paste with 140 com. of Water and 24 ccrn. of hydrochloric acid (22 B.) the resulting paste is cooled by the ad dit-ion of 150 gr. of ice, and there is added thereto a solution of 8 gr. of sodium nitrite dissolved in 50 com. of Water; the resulting mixture is introduced, With stirring, into 524 gr. of tragacanth 60:1000, and thereafter there are added 60 gr. of aluminum sulfate 1 :1 dissolved in Water. Before use, there are added to the composition 20 gr. of sodium phosphate.

Thus a bright claret-red shade is obtained which resists very well the action of soap, sodium carbonate and alkalies. lhe dyestufi has the probable formula:

OH 0.0Ha

3 N-H C- N 1 i t t I a If in the foregoing examples the 2-amino-4- benzoylamino-1-methoxybenzene is replaced for instance by:

' 2-amino-4:-benzoylamino-l-ethoxybenzene menace 2 aminol-bemoylamino-l-benzyloxybenzene or 2 aminot-benzoylamino 1 phenoxybenzene or by the derivatives of these compounds substituted in the benzoyl group, quite similar dyestufis are obtained.

Dyestuffs which give in general a somewhat more bluish hue are produced it the 2.3-hydroxynaphthoic acid -4-chloro-2-toluidide as used in Example 2 is for instance replaced by equivalent quantities of 2.3-hydroXynaphthoic acid-p-anisidide 2.3l1ydr0xynaphthoic acid-2-chloro-4canisidide (Cl:NH:OCH =2: l:1)

2.3-hydroxynaphthoic acid-S-chloro--anisidide (Cl NH ()CH =3 4t: 1)

2.3-hydroxynaphthoic acid-3-nitro-t-anisidide. (N() :NH:OCH =3:4:1)

2.3-hydroxynaphthoic acid-2-phenoXy-1- anilide 2.3 hydroxynaphthoic acid l phehoXy-lanilide 2.3-hydroxyna-phthoic acid-@benzyloxy-lanilide 2.3 hydroxynaphthoic acid 0c naphthylamide or I 2.3 hydroxynaphthoic acid -[3- naphthylamide.

The last mentioned body gives a claret-red tint of a more reddish hue.

vVe claim:

1. The process of producing azo dyestuffs, consisting in coupling arylainides of 2-hydroxynaphthalene-3-carboxylic acid With diazotized bases of the following constitution:

wherein X represents hydrogen or a substituent, R an alkyl-group, aryl group or aralkyl group.

2. Process of producing azodyestuffs, consisting in coupling arylamides of 2-hydroxynaphthalene-3-carboxylic' acid With diazotized 2-a1nino-4-benz oylamino-l-methoxybenzene.

3. Process of producingazo dyestufl's, consisting in coupling 2.3-hydroxynaphthoic acid-5-chloro-2-methoxy-l-anilide of the fob lowing constitution:

with diazotized bases of the following constitution R1 6. X K ,-NHa XV):

wherein X represents hydrogen or a substituent, R, an alkyl-group, aryl group or aralkyl group.

4. As new products, azo dyestuffs of the following formula:

wherein X represents hydrogen or a substituent and R, an alkylarylor aralkyl group, being claret-red powders, insoluble in water, soluble in concentrated sulfuric acid with an intense blue-violet color, the coloring matters, when produced on the fibre,

giving claret-red tints of good fastness to light and kier-boiling.

6. Process for the production of a new azo dyestuff which comprises coupling 2-h droX- ynaphthalene 3 carboxylic acid-5-ch 0ro-2- methoxy-l-anilide of the formula:

2 O-N 1 4 II I 5 O H with diazotized 2-amino-4c-benzoylamino-1- methoxy benzene.

7. As new products, azo dyestuffs having the general formula O CHs N-H -|(|J-Nary1 being, in the'dry powdered state, claret-red powders insoluble in water, soluble in concentrated sulfuric acid with an intense blueviolet color, the'dyestuifs, when produced on the fiber, giving claret-red tints of good fastness to light and to kier-boiling.

8. As a new product the azo dyestuff having the probable formula In testimony whereof, we afiix our signatures.

DR. HERMANN WAGNER. DR. OTTO SOHST.

CERTIFICATE OF CORRECTION.

Patent No. 1,681,602. Granted August 21, 1928, m

HERMANN WAGNER ET AL.

It is hereby certified that error appears in the printed specification ofthe above numbered patent requiring correction as follows: Page 1, line 5, for the word "for" read "or"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 8th day of January. A. D. .1929.

M. J. Moore, (Seal) Acting Commissioner of Patents. 

